CN102617767B - Synthesis method of acrylate crystalline polymer with lateral chain - Google Patents
Synthesis method of acrylate crystalline polymer with lateral chain Download PDFInfo
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- CN102617767B CN102617767B CN 201210035329 CN201210035329A CN102617767B CN 102617767 B CN102617767 B CN 102617767B CN 201210035329 CN201210035329 CN 201210035329 CN 201210035329 A CN201210035329 A CN 201210035329A CN 102617767 B CN102617767 B CN 102617767B
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- acrylate
- fatty alcohol
- crystalline polymer
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Abstract
The invention belongs to the field of chemical industry, and particularly discloses a synthesis method of an acrylate crystalline polymer with a lateral chain. The synthesis method comprises the step: carrying out ultraviolet light irradiation on long-straight-carbon-chain fatty alcohol acrylate monomer and a free radical photoinitiator in a mixed solvent to form a crystalline powdery polymer, wherein the mixed solvent comprises an excellent solvent capable of dissolving the long-straight-carbon-chain fatty alcohol acrylate monomer and the polymer thereof as well as a poor solvent incapable of dissolving the polymer of the long-straight-carbon-chain fatty alcohol acrylate monomer, and the volume ratio of the excellent solvent to the poor solvent is (80:20)-(60:40). According to the invention, the energy consumption is low, the conditions are mild, and the efficiency is high; the melting point of the acrylate crystalline polymer with the lateral chain can be improved by 3-6 DEG C; and the acrylate crystalline polymer with the lateral chain can be successfully applied to a photo-curable paint formula, so as to improve the normal-temperature adhesion and hardness of a cured film as well as improve the high-temperature adhesion performance of the cured film.
Description
Technical field
The present invention relates to chemical technology field, more particularly, the present invention relates to have the synthetic method of the acrylate crystalline polymer of side chain.
Background technology
Acrylate crystalline polymer with side chain generally is based on armorphous main chain backbone, and the polymkeric substance of crystallization can occur side chain.This base polymer is when it exists below crystalline melt point, polymkeric substance is crystal habit, show as solid during Individual existence, and while mixing with other liquid resins, monomer, because the non-crystalline areas of polymkeric substance is made mixed system present the high heterogeneous characteristic of viscosity by liquid resin or monomer local dissolution.Once be heated to have near the acrylate crystalline polymer fusing point of side chain, the melting of crystallizable side chain crystalline region, this polymkeric substance can make again mixed system viscosity sharply reduce, after cooling, the polymkeric substance dissolved in system can recover the crystallizable side chain state again, and crystalline region is scattered in mixed system with the scale that is close to nanoscale.This rheological properties of acrylate crystalline polymer with side chain has been given the numerous processing of high molecular material operational characteristiies that comprise composite processing, be applied to field of compound material, can keep the initial viscosity that polymer paste is higher, be convenient to hanging, and the process that is heating and curing forms than low viscosity state, can make again slurry better infiltrate out-phase framework material and packing material, form interface bond strength preferably.While being applied to coating system, the acrylate crystalline polymer with side chain is scattered in solidified coating with the microcell crystallization phases, can improve coating machine intensity and to the barrier property of water, oxygen.Be applied to powder coating systems, under normal temperature, powder keeps preventing that with its crystallization property adhesion morbid state from occurring, after spraying, is heated to have near the acrylate crystalline polymer fusing point of side chain, form low viscosity fluid, be beneficial to wetting base material and coating self levelling film forming.Be applied to aqueous coating system, acrylate crystalline polymer and other mixed with resin with side chain, be scattered in water, crystalline structure in dispersed particle can hinder coalescent between particle, be beneficial to the deflocculate stability that improves aqueous dispersion, once, after application, through simply heating, can obtain good levelling film-forming properties.
At photo-cured coating, printing ink, adhesive area, because photocuring formation coating, China ink layer, glue-line are the crosslinked polymer networks that moment forms under ultraviolet light irradiation, usually be accompanied by higher string stress, cross-linked coating, China ink layer, glue-line face the challenge to the adhesivity of base material, the morbid state such as " quick-fried film " usually occur, come off, especially when the Impact Test of experience cold cycling, the string stress of cross-linked network often is exaggerated, and defect is more obvious.Existing solution mainly, by adding inert polymer, is served as polymer carrier, alleviates the cross-linked network string stress.The method is also a kind of enlightenment for the application of acrylate crystalline polymer in photo-cured coating, printing ink, tackiness agent with side chain.Each molecular chain of acrylate crystalline polymer with side chain has numerous overlength normal carbon chains, can the unit molecule crystallization, also but polymolecular is coalescent, side chain effect and form the polymolecular crystallization each other, present at normal temperatures the solid crystal state, be heated to tens or up to a hundred degrees centigrade the time, crystallization melting, volumetric expansion.This acrylate crystalline polymer with side chain is made an addition in photo-cured coating, printing ink, adhesive formulation, likely reduce the string stress of cured film, improve normal temperature sticking power, hardness.Under heating status, the dispersed crystalline polymer melt in the photocuring film becomes the microfacies dispersion area, and relieve stresses strengthens cured film high temperature adhesion property, prevents quick-fried film, comes off.
With regard to the acrylate crystalline polymer structure with side chain, the side chain that crystallization can occur usually is the comparatively regular and simple long chain alkyl group such as sufficiently long normal carbon chain, polyoxyethylene chain, long fluorocarbon chain, usually side chain lengths need reach more than 5 times of main chain repeating unit atomicity, and side is conducive to form crystallizable side chain.Under main polymer chain constraint, these long-chain side groups can be automatically coalescent and formation crystallization.Backbone structure with acrylate crystalline polymer of side chain can have broad variety, comprise the Aromatic polyester of harder main chain, poly-propine etc., the polyacrylic ester of more flexible main chain, polyacrylate, polyacrylamide, cyclic olefin polymer, and the Mierocrystalline cellulose of half Flexible Main chain structure etc.Can be connected by various ways between crystallinity side chain and main polymer chain, comprise ester group, amide group, urethano, ehter bond, C-C key, organosilicon radical, ionic group etc.Too the main polymer chain of rigidity may restrict the motion of side chain and mutually close, is unfavorable for crystallizable side chain.The more acrylate crystalline polymer with side chain of research report surely belongs to homopolymer or the multipolymer of speciality carbon chain acrylate or corresponding methacrylic ester, but methacrylate polymers is because of the steric hindrance of main chain methyl, main chain is too stiff, hinder the motion crystallization of side chain, cause the crystalline melt temperature of this base polymer to reduce.Relatively, the fusing point of methacrylate polymers is generally than the low approximately 15 ℃ of left and right of the crystalline melt point of acrylic ester polymer for the straight-chain fatty alcohol acrylate of long carbochain fatty alcohol methacrylic ester and equal length.Crystalline melt temperature and its side chain carbon number of long carbochain fatty alcohol acrylic ester polymer have substantial connection, the side chain carbon number is more, acrylate crystalline polymer fusing point with side chain is higher, when the fatty alcohol carbonatoms reaches 10 when above, formed acrylic ester polymer can form crystallizable side chain near room temperature.Long carbochain fatty alcohol itself as presoma also has definite melting point, and same how much relevant with carbon atom.Generally after forming acrylic ester polymer, the polymer lateral chain crystalline melt point will reduce several years to tens degree the fusing point of presoma long chain aliphatic alcohol, and carbonatoms is fewer, this gap is larger, general reach 18 when above when the long chain aliphatic alcohol carbonatoms, polyacrylic ester crystallizable side chain melting temperature hangs down approximately 4 ~ 8 ℃ than long chain aliphatic alcohol fusing point.For straight chain octadecanol acrylate, corresponding polymer lateral chain crystalline melt temperature is 50 ℃, and the crystalline melt temperature of straight chain two Lauryl Alcohol acrylic ester polymerizations is elevated to 60 ℃.The polymer pendant groups normal carbon chain is longer, and the degree of crystallinity of polymkeric substance is higher, and fusing point is also higher.
The acrylate crystalline polymer with side chain of current report be take overlength normal carbon chain fatty alcohol acrylic ester polymer as main, side chain crystallinity is remarkable, and easily control, its synthetic method is generally direct solution polymerization, by overlength normal carbon chain fatty alcohol acrylate monomer at benzene, toluene, dimethylbenzene, ethyl acetate, in the conventional single solvent such as pimelinketone, using Diisopropyl azodicarboxylate or benzoyl peroxide as polymerization starter, obtain polymers soln by the heated polymerizable method, then by aftertreatments such as precipitation purify, obtain the acrylate crystalline polymer with side chain of solid state.This traditional method long reaction time, need heating, and energy consumption is high, and the polymerisate separation and purification is loaded down with trivial details.Solution reaction later stage system viscosity is higher, causes polymerisation conversion not high.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide under a kind of normal temperature condition and prepare and there is the method for the acrylate crystalline polymer of side chain from purifying fast.Specifically, exactly will long normal carbon chain fatty alcohol acrylate monomer in the mixed solvent formed by good solvent and poor solvent, before polymerization starts, system is the homogeneous solution state substantially, by ultraviolet light irradiation, start rapidly polymerization, formed polymerisate solvability in mixed solvent is poor, coalescently be Powdered and separate out from solvent, react 3
~6 hours, polymer yield can reach more than 90%, and gained polymerisate fusing point is a little more than obtain the acrylate crystalline polymer with side chain by traditional thermopolymerization.
Above-mentioned purpose of the present invention is achieved by following scheme:
Selecting carbonatoms is 18
~the monobasic overlength normal carbon chain fatty alcohol acrylate of 32 even numbers has the principal monomer of the acrylate crystalline polymer of side chain as acquisition, comprise positive octadecanol acrylate, positive eicosanol acrylate, positive two Lauryl Alcohol acrylate, positive tetracosa carbon alcohol acrylate, positive 26 carbon alcohol acrylate, positive octacosanol acrylate, positive 30 carbon alcohol acrylate, positive three Lauryl Alcohol acrylate, and in above acrylate a kind of, two or more form mix monomer.
For improving the consistency of polymerisate and other resins, can select the monomer that a small amount of polarity is relatively high to participate in copolymerization as the second monomer, the acrylate crystalline polymer with side chain of a small amount of polar group is carried in acquisition, concrete high polarity the second monomer mainly refers to the acrylic monomer with carboxyl, hydroxyl, includes but not limited to vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate etc.Above-mentioned the second monomer in polyreaction as option.
Light trigger of the present invention refers to wavelength 300
~the light activated crack type photoinitiator of 400 nm ultraviolet, under ultraviolet light irradiation, the rapid cracking of light trigger becomes Active Radicals Produced, initiating methacrylates monomer rapid polymerization.Light trigger comprises free radical type and cationic, and latter's application is relatively less, and only is applicable to the monomer of special construction.Radical photoinitiator refers to that photodissociation produces Active Radicals Produced, comprise hydrogen-capture-type light initiator and the higher crack type photoinitiator of photoresponse efficiency that light reaction is lower, the present invention adopts the crack type photoinitiator that efficiency is higher, chemical structure mainly comprises alpha-hydroxyalkyl phenyl ketone, alpha-aminoalkyl phenyl ketone, sweet-smelling formacyl phosphorus oxidation compound etc., common business sells crack type photoinitiator Darocur 1173, Irgacure 184, Irgacure 651, Darocur 2959, Irgacure 369, Irgacure 907, Darocur TPO, Irgacure 819 etc., and Darocur 1173 light triggers with alpha-hydroxyalkyl phenyl ketone structure are more excellent.Except this it, also have multiple crack type photoinitiator also to be applicable to this synthetic method, as Darocur MBF, Irgacure 754, Irgacure 651 etc.Above-mentioned crack type photoinitiator also can two or more form the mixed light initiator system.Also can form the mixed light initiator system by above-mentioned crack type photoinitiator and hydrogen-capture-type light initiator.Above-mentioned light trigger title has adopted photocuring technology field convenience goods code name title the most, and each light trigger is concrete chemical structure and the systematic name of correspondence all, and as fine chemicals, they also have the name of other different modes on market.
Mixed solvent is one of key of method, and overlength normal carbon chain fatty alcohol acrylate monomer is due to longer low-pole carbon-chain structure, causes in multiple high polar solvent compatibility not good, affects dispersion effect and polymerization efficiency.On the other hand, overlength normal carbon chain fatty alcohol acrylic ester polymer, due to lower polarity, does not dissolve in a lot of high polar solvents yet.Thereby select merely poor solvent as reaction medium, and can cause monomer and demixing of solvents, even solid monomer can't dissolve dispersion at all, can't carry out effective polyreaction.Select the weak benzene series solvent of polarity or ester class, ketone, ether solvent fine overlength normal carbon chain fatty alcohol acrylate monomer to be dissolved fully.Yet, only select good solvent as polymerization reaction medium, the polymkeric substance generated also may well be dissolved in wherein, polymerization process belongs to the typical solution polymerization, polymerisate is Precipitation from solution voluntarily, reaction later stage system viscosity is high, and polymerisation conversion is not high, also is unfavorable for making excuses aftertreatment and separates.By the mix and match of good solvent and poor solvent, control suitable proportion, can guarantee that the fine dissolving therein of overlength normal carbon chain fatty alcohol acrylate monomer disperses, and the polymerisate formed is because the effect of high polar solvent will be separated out automatically from mixed solvent.The good solvent of present method indication is mainly benzene series solvent, esters solvent, ketones solvent, ether solvent, include but not limited to benzene,toluene,xylene, tetramethyl-benzene, dimethyl phthalate, ethyl acetate, n-butyl acetate, 2-ethyl hexyl ethanoate, 2-butanone, pimelinketone, 2-heptanone, isophorone, di-n-butyl ether etc., and using the benzene aromatic hydrocarbon solvent as solvent more preferably.Poor solvent mainly refers to the alcoholic solvent that type is higher, and moieties is unsuitable excessive, includes but not limited to methyl alcohol, ethanol, Virahol, 1,2-PD etc.During the modulation mixed solvent, the volume ratio of good solvent and poor solvent can be at 90:10
~between 50:50, adjust, more preferably volume ratio is 80:20
~60:40.
Polymerization process of the present invention is that monomer solution starts reaction under ultraviolet light irradiation, and the ultraviolet source adopted is power 40
~the medium pressure mercury lamp of 2000W, its stronger emission wavelength is 365nm, has and utilizes the emission ultraviolet wavelength be worth to be positioned at 300
~between 400nm, according to ultraviolet lamp self power and light source, apart from the distance of reaction system, select to adjust light intensity, what the present invention was suitable for is positioned at 300
~ultraviolet light intensity between 400nm is 1.5
~80 mW/cm
2.When ultraviolet ray intensity is too low, the photon energy deficiency, can't the effectively start photopolymerization; When the UV-light energy is too high, follow the infrared heating of light source serious, cause the polymerization system heat effect remarkable, may cause low boiling point solvent volatilization loss and unmanageable side reaction to occur.As illumination condition more preferably, ultraviolet light intensity 3.0
~12mW/cm
2more excellent.For synthesizing of 100g solution reaction scale, adopt the medium pressure mercury lamp of 400 W, with 9.6 mW/cm
2ultraviolet light intensity radiation polymerization 3 hours, direct filtration obtains crystalline polymer, polymer yield reaches 92%.Synthetic gained polymerisate adopts determine with dsc method fusing point and degree of crystallinity, with gel permeation chromatograph, measures polymericular weight.The paint solidification performance test is carried out according to CNS.
Compared with prior art, the present invention has following beneficial effect:
1) adopt the preparation of gentle photopolymerization means to there is the acrylate crystalline polymer of side chain, under room temperature condition, the solution-precipitation polymerization of long normal carbon chain fatty alcohol acrylate fast, now for traditional thermopolymerization, energy consumption of the present invention is low, mild condition, and efficiency is high.
2) relatively traditional crystallizable side chain acrylic ester polymer synthetic method, design implementation of the present invention light-initiated precipitation polymerization technique, polymerisate is directly separated out with the crystalline powder form from solvent, and the aftertreatment work such as separation, purifying become very simple, only need simple filtration.
3) have the acrylate crystalline polymer of side chain with respect to the thermal polymerization method gained, adopt room temperature efficiency light polymerization synthesizing mean of the present invention, the fusing point that gained has the acrylate crystalline polymer of side chain can improve 3
~6 ℃.
The acrylate crystalline polymer that 4) will have a side chain is successfully applied to the photo-cured coating formula, improves cured film normal temperature sticking power and hardness, has also improved the high temperature adhesion property of cured film.
Embodiment
embodiment 1 ~ 15
Long normal carbon chain fatty alcohol acrylate monomer foundation wherein long normal carbon chain carbonatoms is used respectively code name C
na means, n wherein means the carbonatoms of overlength normal carbon chain, and the corresponding relation of code name and monomer title is listed in table 1.
Table 1 monomer code name C
nthe corresponding relation of A and title
Other raw material code names are:
AA-vinylformic acid;
HEA-Hydroxyethyl acrylate;
Darocur 1173-2-hydroxy-2-methyl-1-phenyl-1-acetone
Darocur TPO-phenylbenzene-(2,4,6-Three methyl Benzene formyl) phosphorus oxide
According to the synthetic acrylate crystalline polymer with side chain of the correlated condition of table 1, they be by long normal carbon chain fatty alcohol acrylate monomer and free radical photo-initiation in mixed solvent, through ultraviolet light irradiation, formation crystalline powder shaped polymer; Described mixed solvent is to dissolve the good solvent of long normal carbon chain fatty alcohol acrylate monomer and polymkeric substance thereof and the mixed solvent of the poor solvent of the polymkeric substance that can not dissolve long normal carbon chain fatty alcohol acrylate monomer, specifically will long normal carbon chain fatty alcohol acrylate monomer C
na, the second monomer, light trigger are dissolved in the mixed solvent of aromatic hydrocarbons/alcohol, C
na monomer 20 g, mixed solvent 80 g, the light trigger consumption was 3% of monomer solubilizing agent gross weight, with 1000 W medium pressure mercury lamp irradiation 3 hours.Under each condition, gained polymerisate character is listed in table 2.
Table 2 has the acrylate crystalline polymer synthetic example of side chain
reference examples 1 ~ 5
Example, be to carry out C under the reacting by heating condition in contrast
nthe solution polymerization of A monomer, C
na monomer consumption is 20.0 g, and toluene is solvent, consumption 80 g, Diisopropyl azodicarboxylate is thermal polymerization, consumption 1.5 g, 80 ℃ of temperature of reaction, polymerization time 6 hours, reaction slowly proceeds to reaction solution in 500 ml methyl alcohol after finishing, separate out polymer solids, filter, then, with the toluene heating for dissolving, carry out the redeposition purifying, remove unreacted monomer, weigh after drying.Ditto carry out dependence test.Reference examples implementation condition and the results are shown in Table 3.
Table 3 reference examples condition and result.
application examples 1
Embodiment 13 resulting polymers are added in the photo-cured coating of high rigidity formula, detect light solidifying coating normal temperature hardness and sticking power, and the coating adhesion under 60 ℃.Photo-cured coating formula materials used comprises six functional polyurethanes acrylate B605(Guangzhou Boxing chemical industry), flexible epoxy acrylate B151(Guangzhou Boxing chemical industry), aliphatics two functional polyurethanes acrylate EB270(cyanogen specializations), 1, part by weight 0.4% in 6-hexylene glycol double methacrylate HDDA, light trigger Darocur 1173, flow agent BYK-306(formula), there is the acrylate crystalline polymer of side chain etc., the paint formulation roller coat is on ABS-PC test sheet material, actual measurement coat-thickness 55 μ m are 115 mW/cm through light intensity
2ultraviolet light irradiation 8 seconds, the curing cross-linked film forming, solidified coating sticking power carries out with reference to GB GB/T 9286-1998, cross-hatching, adhesive tape pulls open, and observes the coating shedding situation, by excellent, to bad, is divided into 0 ~ 5 grade.0 grade of optimum.The solidified coating determination of pencil hardness carries out with reference to GB GB6739-86.Correlated condition is listed in table 4, and test result is listed in table 5.
application examples 2
Reference examples 5 resulting polymers are added to respectively in the photo-cured coating of high rigidity formula, detect light solidifying coating normal temperature hardness and sticking power, and the coating adhesion under 60 ℃.Photo-cured coating formula materials used comprises six functional polyurethanes acrylate B605(Guangzhou Boxing chemical industry), flexible epoxy acrylate B151(Guangzhou Boxing chemical industry), aliphatics two functional polyurethanes acrylate EB270(cyanogen specializations), 1, part by weight 0.4% in 6-hexylene glycol double methacrylate HDDA, light trigger Darocur 1173, flow agent BYK-306(formula), there is the acrylate crystalline polymer of side chain etc., the paint formulation roller coat is on ABS-PC test sheet material, actual measurement coat-thickness 55 μ m are 115 mW/cm through light intensity
2ultraviolet light irradiation 8 seconds, the curing cross-linked film forming, solidified coating sticking power carries out with reference to GB GB/T 9286-1998, cross-hatching, adhesive tape pulls open, and observes the coating shedding situation, by excellent, to bad, is divided into 0 ~ 5 grade.0 grade of optimum.The solidified coating determination of pencil hardness carries out with reference to GB GB6739-86.Correlated condition is listed in table 4, and test result is listed in table 5.
table 4: formula
table 5: light solidifying coating test result
From table 5, the light solidifying coating (application examples one) of the acrylate crystalline polymer with side chain that adds the present invention to synthesize, with respect to the light solidifying coating that does not have the addition polymerization compound, can significantly improve normal temperature hardness, normal temperature sticking power and the adhesion property that is heated of light solidifying coating; With respect to the acrylate crystalline polymer with side chain (application examples two) that adds traditional thermopolymer to obtain, resulting polymers molecular weight of the present invention is higher, can more effectively improve hardness of paint film and the adhesion property that is heated in the cured film cross-linked network.
Claims (6)
1. the synthetic method with acrylate crystalline polymer of side chain is characterized in that: it be by long normal carbon chain fatty alcohol acrylate monomer and free radical photo-initiation in mixed solvent, through ultraviolet light irradiation, form the crystalline powder shaped polymer; Described mixed solvent is to dissolve the good solvent of long normal carbon chain fatty alcohol acrylate monomer and polymkeric substance thereof and the mixed solvent of the poor solvent of the polymkeric substance that can not dissolve long normal carbon chain fatty alcohol acrylate monomer, and described long normal carbon chain fatty alcohol acrylate monomer refers to that carbonatoms is 18
~the long normal carbon chain fatty alcohol acrylate monomer of 32 even numbers;
The combination of described good solvent and poor solvent and both volume ratios are a kind of in following four kinds of combinations:
Toluene: methyl alcohol=90:10;
Toluene: ethanol=70:30;
Ethyl acetate: methyl alcohol=70:30;
Pimelinketone: methyl alcohol=80:20.
2. the synthetic method with acrylate crystalline polymer of side chain according to claim 1 is characterized in that: long normal carbon chain fatty alcohol acrylate monomer is the straight chain fat monobasic primary alconol acrylate that carbonatoms is 18～32 even numbers.
3. the synthetic method with acrylate crystalline polymer of side chain according to claim 2 is characterized in that: long normal carbon chain fatty alcohol acrylate monomer is the straight chain fat monobasic primary alconol acrylate that carbonatoms is 22～28 even numbers.
4. the synthetic method with acrylate crystalline polymer of side chain according to claim 2, it is characterized in that: described free radical photo-initiation comprises the light activated crack type photoinitiator of wavelength 300～400 nm ultraviolet.
5. the synthetic method with acrylate crystalline polymer of side chain according to claim 4, it is characterized in that: described free radical photo-initiation is the light trigger with at least one structure in alpha-hydroxyalkyl phenyl ketone structure, alpha-amine alkyl phenyl ketone structure, sweet-smelling formacyl phosphorus oxide structure.
6. the synthetic method with acrylate crystalline polymer of side chain according to claim 1, it is characterized in that: in mixed solvent, also add the acrylate or the vinylformic acid that carry carboxyl to participate in copolymerization as the second monomer, described the second monomer is 1:15～1:10 with the part by weight of long normal carbon chain fatty alcohol acrylate monomer.
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